JPH02142766A - Production of aziridine compound - Google Patents
Production of aziridine compoundInfo
- Publication number
- JPH02142766A JPH02142766A JP63293665A JP29366588A JPH02142766A JP H02142766 A JPH02142766 A JP H02142766A JP 63293665 A JP63293665 A JP 63293665A JP 29366588 A JP29366588 A JP 29366588A JP H02142766 A JPH02142766 A JP H02142766A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- formula
- reaction
- alkanolamine
- aziridine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 aziridine compound Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 239000000575 pesticide Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001541 aziridines Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940102253 isopropanolamine Drugs 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は一般式（Ａ）で表されるアルカノールアミンを
触媒の存在下に気相分子内脱水反応せしめて一般式（Ｂ
）で表されるアジリジン化合物を製造する方法に関する
。Detailed Description of the Invention [Industrial Field of Application] The present invention involves subjecting an alkanolamine represented by the general formula (A) to a gas-phase intramolecular dehydration reaction in the presence of a catalyst to obtain the alkanolamine represented by the general formula (B).
) The present invention relates to a method for producing an aziridine compound represented by:
（式中のＲ，Ｒ’は各々式（Ａ）と同じである。 ）
で表されるアジリジン化合物を製造するに際し、該アル
カノールアミンを高温、減圧下で、外径３〜１０＋＋＋
ｍ、長さが外径の０．５〜２．０倍の（式中のＲ，Ｒ’
は各々水素、メチル基およびエチル基の中から選ばれろ
。）
アジリジン化合物は反応性の高いアミノ基を有する環式
アミンであり、医薬、農薬等の原料として、また繊維処
理剤であるアミン系ポリマーの原料としてすでに産業界
で広く用いられている非常に有用な化合物である。本発
明は、この利用価値の高いアジリジン化合物を効率よく
製造するに優れた方法を提供するものである。(In the formula, R and R' are each the same as in formula (A).) When producing the aziridine compound represented by the formula (A), the alkanolamine is heated at high temperature and under reduced pressure to form an alkanolamine with an outer diameter of 3 to 10+++.
m, the length is 0.5 to 2.0 times the outer diameter (R, R' in the formula
are each selected from hydrogen, methyl, and ethyl. ) Aziridine compounds are cyclic amines with highly reactive amino groups, and are extremely useful and are already widely used in industry as raw materials for medicines, agricultural chemicals, etc., and as raw materials for amine-based polymers used as fiber treatment agents. It is a chemical compound. The present invention provides an excellent method for efficiently producing this highly useful aziridine compound.
［従来の技術］
アルカノールアミンからアジリジン化合物を製造する方
法としては、液相中でアルカノールアミンの硫酸エステ
ルを濃アルカリで処理しアジリジン化合物を製造する方
法が一般的によく知られており、この方法はエチレンイ
ミンの製造方法として既に工業化されている。この方法
は、副原料として硫酸及びアルカリを大量に用いるため
生産性が低く、更には利用度の低い無機塩が大量に副生
じ、工業的には多くの欠点を有するものである。[Prior Art] A generally well-known method for producing an aziridine compound from an alkanolamine is a method in which the sulfuric acid ester of an alkanolamine is treated with a concentrated alkali in a liquid phase to produce an aziridine compound. has already been industrialized as a method for producing ethyleneimine. This method uses a large amount of sulfuric acid and alkali as auxiliary raw materials, resulting in low productivity and also produces a large amount of inorganic salts with low utilization, so it has many disadvantages from an industrial perspective.
最近、この上うな液相法の欠点を解決すべ（、副原料を
全く用いずにアルカノールアミンを触媒の存在下、気相
分子内脱水反応せしめ、直接アジリジン化合物を製造す
る試みがいくつか報告きれている。それらの例として、
例えば、ヨーロッパ公開特許第２２７，４６１号、同第
２２８，８９８号、同第２３０，７７６号各公報に優れ
た触媒が開示されている。しかし、何れの場合も触媒組
成が開示されているだけであり、効率よくアジリジン化
合物を製造するための触媒の形状については未だ開示さ
れていない。Recently, several attempts have been made to overcome these drawbacks of the liquid phase method (i.e., to directly produce aziridine compounds by subjecting alkanolamines to intramolecular dehydration in the gas phase in the presence of a catalyst without using any auxiliary raw materials). Examples of these are:
For example, excellent catalysts are disclosed in European Patent Publication Nos. 227,461, 228,898, and 230,776. However, in each case, only the catalyst composition is disclosed, and the shape of the catalyst for efficiently producing an aziridine compound is not yet disclosed.
アルカノールアミンの気相分子内脱水によるアジリジン
化合物の生成反応は平衡反応であって原料アルカノール
アミン分圧が小さいほどアジリジン化合物の生成に有利
である。また生成したアジリジン化合物の捕集の面から
はキャリアーガスを用いない減圧での反応が非常に有利
である。従って工業的なプロセスでは１０〜２００ ｍ
ｍＨｇの減圧での反応が望ましい。この際問題になるこ
とは触媒層の圧力損失で、これが大きいと減圧した効果
が損なわれて原料アルカノールアミン分圧が大きくなり
、その結果環化生成物が副生じて目的とするアジリジン
化合物の選択性の低下をきたす。ざらには触媒層入口圧
が大きくなりすぎると蒸発器の温度を高くしなければな
らず、加熱媒体として有利な蒸気を使用することが困難
となる。これらの問題の解決のためには触媒層の圧力損
失は小さくすることが求められる。The reaction for producing an aziridine compound by gas-phase intramolecular dehydration of alkanolamine is an equilibrium reaction, and the smaller the partial pressure of the raw alkanolamine, the more advantageous it is for producing the aziridine compound. Furthermore, from the viewpoint of collecting the produced aziridine compound, the reaction under reduced pressure without using a carrier gas is very advantageous. Therefore, in industrial processes 10 to 200 m
Reactions at reduced pressures of mHg are preferred. The problem in this case is the pressure loss in the catalyst layer, and if this is large, the effect of pressure reduction will be impaired and the partial pressure of the raw material alkanolamine will increase, resulting in a by-product of cyclization and the selection of the desired aziridine compound. It causes a decline in sexuality. In general, if the catalyst bed inlet pressure becomes too high, the temperature of the evaporator must be increased, making it difficult to use steam, which is advantageous as a heating medium. In order to solve these problems, it is required to reduce the pressure loss in the catalyst layer.
［発明が解決しようとする課題］
本発明の目的は、圧力損失を可能な限り小さくし、アジ
リジン化合物を効率よく製造する方法を提供することに
ある。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for efficiently producing an aziridine compound while reducing pressure loss as much as possible.
［課題を解決するための手段］
本発明者らはアルカノールアミン類の気相分子内脱水反
応による製造方法について鋭意研究した結果、アジリジ
ン化合物を高効率で製造できる工業的に非常に優れた方
法を完成するに至った。即ち、本発明は前記一般式（Ａ
）で表されろアルカノールアミンを触媒の存在下に気相
分子内脱水反応せしめて前記一般式（Ｂ）で表されろア
ジリジン化合物を製造するに際し、該アルカノールアミ
ンを高温、減圧下で、外径３〜１０ｍｒＱ、長きが外径
の０． ５〜２．０倍の円柱の外形を有し、がっその縦
軸方向にその体積が全体の１０％〜８０％の範囲である
貫通部分を有する形状の触媒を用いるアジリジン化合物
の製造方法である。以下、本発明の詳細な説明する。[Means for Solving the Problems] As a result of intensive research into a method for producing alkanolamines by gas-phase intramolecular dehydration reaction, the present inventors have discovered an industrially excellent method for producing aziridine compounds with high efficiency. It was completed. That is, the present invention provides the general formula (A
) When producing the aziridine compound represented by the general formula (B) by subjecting the alkanolamine represented by the formula (B) to a gas-phase intramolecular dehydration reaction in the presence of a catalyst, the alkanolamine is subjected to a gas phase intramolecular dehydration reaction in the presence of a catalyst. 3~10mrQ, length is 0. A method for producing an aziridine compound using a catalyst having a cylindrical outer shape of 5 to 2.0 times the size and having a penetrating portion in the longitudinal direction of the cylinder whose volume is in the range of 10% to 80% of the total volume. be. The present invention will be explained in detail below.
本発明で使用する触媒の成分や担体は、例えばアルカノ
ールアミンの気相分子内脱水によるアジリジン化合物の
製造に関する前記公報に記載されているものが使用でき
、特に以下に述べるようなリン系やケイ素系の触媒が好
ましいが、これらに限定されろものではない。As the catalyst components and carriers used in the present invention, those described in the above-mentioned publication regarding the production of aziridine compounds by gas-phase intramolecular dehydration of alkanolamines can be used, and in particular, the following phosphorus-based and silicon-based These catalysts are preferred, but are not limited to these.
・ヨーロッパ公開特許第２３０．７７６号公報に記載の
、一般式 Ｘ −Ｐ ｂＭ ｅＯａ で表わされるリ
ン系の触媒。- A phosphorus-based catalyst represented by the general formula X-PbMeOa described in European Patent Publication No. 230.776.
ここで、Ｘは周期律表におけるＩＩＩ Ａ族元素、ケイ
素、ゲルマニウム、スズ、鉛、アンチモン、ビスマス、
Ｉ族ないし■族の遷移金属元素、ランタニド元素および
アクチニド元素の中から選ばれる１種またはそれ以上の
元素（これらの元素の例としては、Ｂ、ＡＩ、ＴＩ。Here, X is a group IIIA element in the periodic table, silicon, germanium, tin, lead, antimony, bismuth,
One or more elements selected from Group I to Group II transition metal elements, lanthanide elements, and actinide elements (examples of these elements include B, AI, and TI.
Ｓｉ、 Ｓｎ、 Ｓｂ、 Ｂｉ、 Ｃｕ、
Ｚｎ、 Ｃｄ。Si, Sn, Sb, Bi, Cu,
Zn, Cd.
Ｙ、 Ｔｉ、 Ｚｒ、 Ｎｂ、 Ｔａ、 Ｗ
、 Ｍｎ。Y, Ti, Zr, Nb, Ta, W
, Mn.
Ｆｅ、Ｎｉ、Ｌａ、Ｃｅ、Ｅｕ、Ｔｈなどの元素が挙げ
られる）、Ｐはリン、Ｍはアルカリ金属元素および／ま
たはアルカリ土類金属元素の中から選ばれる１種または
それ以上の元素（これらの元素の例としては、Ｌｉ。P is phosphorus, M is one or more elements selected from alkali metal elements and/or alkaline earth metal elements (including elements such as Fe, Ni, La, Ce, Eu, Th, etc.); An example of the element is Li.
Ｎａ、に、Ｒｂ、Ｃｓ、Ｓｒ、Ｂａなどの元素が挙げら
れる）、０は酸素を表す。また、ａ＝１のときｂ＝ｏ、
０１〜６、ｃ＝０〜３の範囲を取り、ｄはａ、 ｂ、
ｃの値および各種構成元素の結合状態により定まる
数値である。0 represents oxygen. Also, when a=1, b=o,
01-6, c=0-3, d is a, b,
It is a numerical value determined by the value of c and the bonding state of various constituent elements.
・ヨーロッパ公開特許第２２８，８９８号公報に記載の
、一般式 Ｘ 、 Ｐ ｂＹ −Ｏａ で表わされる
リン系の触媒。- A phosphorus-based catalyst represented by the general formula X, PbY-Oa, described in European Patent Publication No. 228,898.
ここで、Ｘはアルカリ金属元素および／またはアルカリ
土類金属元素の中から選ばれろ１種またはそれ以上の元
素、Ｐはリン、Ｙはホウ素、アルミニウム、ケイ素、イ
オウ、チタン、銅、イツトリウム、ジルコニラＪ＼、ニ
オブ、タンタル、タングステン、ランタン、セリウｌ、
およびトリウムの中から選ばれる１種またはそれ以上の
元素、０は酸素を表す。Here, X is one or more elements selected from alkali metal elements and/or alkaline earth metal elements, P is phosphorus, and Y is boron, aluminum, silicon, sulfur, titanium, copper, yttrium, zirconyl. J\, niobium, tantalum, tungsten, lanthanum, cerium,
and thorium, and 0 represents oxygen.
また、 ａ＝１のときｂ＝０．０５〜３、Ｃ＝０〜１の
範囲を取り、ｄはａ、 ｂ、 ｃの値および各種構
成元素の結合状態により定まる数値である。Further, when a=1, b=0.05 to 3, C=0 to 1, and d is a numerical value determined by the values of a, b, and c and the bonding state of various constituent elements.
・ヨーロッパ公開特許第２２７，４６１号公報に記載の
、一般式 Ｓ ｉ ａＸｂＹｃｏａ で表わされるケ
イ素系の触媒。- A silicon-based catalyst represented by the general formula S iaXbYcoa described in European Patent Publication No. 227,461.
ここで、Ｘはアルカリ金属元素および／またはアルカリ
土類金属元素の中から選ばれろ１種またはそれ以上の元
素、Ｙはホウ素、アルミニウム、チタン、ジルコニラＬ
＼、スズ、亜鉛およびセリウ１＼の中から選ばれろ１種
またはそれ以上の元素、Ｏは酸素を表す。また、ａ＝１
のときｂ＝０．００５〜１、ｃ＝０〜１の範囲を取り、
ｄはａ、 ｂ、 ｃの値および各種構成元素の結合
状態により定まる数値である。Here, X is one or more elements selected from alkali metal elements and/or alkaline earth metal elements, Y is boron, aluminum, titanium, zirconyl L
\, one or more elements selected from tin, zinc and cerium\, and O represents oxygen. Also, a=1
When b = 0.005 to 1, c = 0 to 1,
d is a numerical value determined by the values of a, b, and c and the bonding state of various constituent elements.
本発明においては触媒の形状は外径３〜１０ｍｍ、長さ
が外径の０． ５〜２． ０倍の円柱の外形を有し、か
つその縦軸方向にその体積が全体の１０％〜８０％の範
囲である貫通部分を有する形状でなければならない。こ
れらの形状の条件を満たさない場合には、触媒層の圧力
損失が大きくなって前記の問題が生じる。In the present invention, the shape of the catalyst is 3 to 10 mm in outer diameter and 0.0 mm in length to the outer diameter. 5-2. It must have the outer shape of a 0x cylinder and have a penetrating portion whose volume in the longitudinal axis direction is in the range of 10% to 80% of the whole. If these shape conditions are not met, the pressure loss of the catalyst layer becomes large and the above-mentioned problem occurs.
本発明の実施に当たり、用いる反応器の形式は一般的な
固定床式反応器が用いられる。原料アルカノールアミン
は蒸発器にて気化され、触媒が充填きれた反応器に通じ
る。窒素などの不活性ガスを混合して原料ガスを希釈す
ることも可能であるが、不活性ガスは用いない方が好ま
しい、、好ましくは、反応圧力は１０〜２００ ｍｍＨ
ｇの減圧下、反応温度は３００〜６００℃の範囲が適当
である。In carrying out the present invention, a general fixed bed reactor is used as the reactor type. The raw material alkanolamine is vaporized in an evaporator, and is passed to a reactor filled with a catalyst. Although it is possible to dilute the raw material gas by mixing an inert gas such as nitrogen, it is preferable not to use an inert gas. Preferably, the reaction pressure is 10 to 200 mmH.
The reaction temperature is suitably in the range of 300 to 600°C under a reduced pressure of 1.5 g.
また、原料ガスの空間速度は反応圧力によって異なるが
５０〜２０００ｈｒ”の範囲をとることが出来る。Further, the space velocity of the raw material gas varies depending on the reaction pressure, but can range from 50 to 2000 hr.
［実施例コ
以下、実施例によって本発明をさらに具体的に説明する
。なお、転化率、選択率および単流収率はそれぞれ次の
定義に従った。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the conversion rate, selectivity, and single flow yield were each defined as follows.
アルカノールアミンの転化率＝
アジリジン化合物の選択率＝
アジリジン化合物の単流収率＝
以下に説明する方法によって、原料アルカノールアミン
としてモノエタノールアミンを用いアジリジン化合物と
してエチレンイミンを製造した。Conversion rate of alkanolamine = Selectivity of aziridine compound = Single flow yield of aziridine compound = Ethyleneimine was produced as an aziridine compound using monoethanolamine as a raw material alkanolamine by the method described below.
水酸化カルシラＡ、２． ２２ ｋｇと水酸化ナトリウ
ム１２０ｇを純水１０Ｑに懸濁させ、８５重量％オルト
リン酸１．７３ｋｇを加え、十分に攪拌しながら、加熱
濃縮し、蒸発乾固した。これを空気中１２０℃で１２時
間乾燥粉砕した後、小量の水で十分混練し、外径６ｍｍ
、長き６ｍｍ、肉厚０． ９ｍｍの第１図に示すリング
状に成型し、空気中２００℃で１２時間乾燥した後、７
００℃で５時間焼成→−
して原子比で Ｃａ ＩＰ ０．５Ｎ ａ ｏ□ なろ
組成の触媒をえた。Calcilla hydroxide A, 2. 22 kg and 120 g of sodium hydroxide were suspended in 10Q of pure water, 1.73 kg of 85% by weight orthophosphoric acid was added, and the suspension was heated and concentrated with thorough stirring and evaporated to dryness. After drying and pulverizing this in air at 120°C for 12 hours, it was thoroughly kneaded with a small amount of water, and the outer diameter was 6 mm.
, length 6mm, wall thickness 0. It was molded into a 9 mm ring shape as shown in Figure 1, dried in air at 200°C for 12 hours, and then
The catalyst was calcined at 00° C. for 5 hours to obtain a catalyst having an atomic ratio of Ca IP 0.5N ao□ Naro.
この１．０６Ｒを反応器に設置された内径３０ｍｍのス
テンレス製反応管に充填し熱媒にて４００℃に加熱した
。該管内にモノエタノールアミンを反応管出口圧力１５
０ｍｍＨｇ、空間速度４００ ｈｒ−’で通じ連続反応
を行った。反応開始後２４時間後の反応生成物をガスク
ロマトグラフで分析定量した結果を、表−１に示した。This 1.06R was filled into a stainless steel reaction tube with an inner diameter of 30 mm installed in a reactor and heated to 400° C. with a heating medium. Monoethanolamine was introduced into the tube at a reaction tube outlet pressure of 15
Continuous reaction was carried out at 0 mmHg and a space velocity of 400 hr-'. Table 1 shows the results of analyzing and quantifying the reaction product 24 hours after the start of the reaction using a gas chromatograph.
丸丘五−２−】
触媒のＷの値を変えた以外は、実施例１と同様に触媒を
調製し反応を行なワた。反応条件及び結果を表−１に示
した。Maruoka 5-2-] A catalyst was prepared and a reaction was carried out in the same manner as in Example 1, except that the value of W in the catalyst was changed. The reaction conditions and results are shown in Table-1.
旧設１
実施例１の触媒の形状を、外径６ｍ＋ｎ、長さ６Ｉの円
柱状に成型した以外は実施例１と全く同様にして反応を
行なった。反応条件及び結果を表−１にボした。Old facility 1 A reaction was carried out in exactly the same manner as in Example 1, except that the catalyst of Example 1 was molded into a cylindrical shape with an outer diameter of 6 m+n and a length of 6 I. The reaction conditions and results are shown in Table-1.
実淘１１−４
以下に説明する方法によって、原料アルカノールアミン
としてイソプロパツールアミンを用いアジリジン化合物
としてプロピレンイミンを製造した。Example 11-4 Propylene imine was produced as an aziridine compound using isopropanolamine as a raw material alkanolamine by the method described below.
硝酸セシウム３５０ｇ、水酸化ナトリウ１＼８ｇおよび
８５重量％リン酸１８４ｇを純水６９に溶解し、担体と
してシリカゲル１． ２ｋｇを加え、さらに硝酸アルミ
ニウム７．６ｇを加えて加熱濃縮し、１２０℃で１２時
間乾燥した後粉砕し、小量の水を加えて十分混練し、外
径７Ｉ、長き７ｍｍ、肉厚１ｍｍの第２図に示す形状に
成型し、空気中２００℃で１２時間乾燥後、７００℃で
４時間焼成して原子比で Ｃ８ｏ、５Ｎａｏ、ｔＰｏ、
ｓＡ ｌｏ、ｏ＋なる組成の触媒をえた。この触媒１．
７７！２を反応器に設置された内径３０ｍｍのステンレ
ス製反応管に充填し熱媒にて４４０℃に加熱した。該管
内にイソプロパツールアミンを反応圧１００ ｍｍＨｇ
、空間速度３００ ｈｒ−１で通じ連続反応を行った。350 g of cesium nitrate, 1\8 g of sodium hydroxide and 184 g of 85% by weight phosphoric acid were dissolved in 69 g of pure water, and 1.8 g of silica gel was used as a carrier. After adding 2 kg of aluminum nitrate and further adding 7.6 g of aluminum nitrate, heating and concentrating, drying at 120°C for 12 hours, crushing, adding a small amount of water and thoroughly kneading, the outer diameter is 7I, the length is 7mm, and the wall thickness is 1mm. It was molded into the shape shown in Fig. 2, dried in air at 200°C for 12 hours, and then fired at 700°C for 4 hours to obtain C8o, 5Nao, tPo, in atomic ratio.
A catalyst with the composition sA lo, o+ was obtained. This catalyst 1.
77!2 was filled into a stainless steel reaction tube with an inner diameter of 30 mm installed in a reactor and heated to 440° C. with a heating medium. Isopropanolamine was placed in the tube at a reaction pressure of 100 mmHg.
, and a continuous reaction was carried out at a space velocity of 300 hr-1.
反応開始後２４時間後の反応生成物をガスクロマトグラ
フで分析定量した結果を、表−１に示した。Table 1 shows the results of analyzing and quantifying the reaction product 24 hours after the start of the reaction using a gas chromatograph.
Ｋ意思−５
触媒の肉厚を１． ４ｍｍに変えた以外は、実施例４と
同様に触媒を調製し反応を行なった。反応条件及び結果
を表−１に示した。K intention-5 Change the wall thickness of the catalyst to 1. A catalyst was prepared and a reaction was carried out in the same manner as in Example 4, except that the diameter was changed to 4 mm. The reaction conditions and results are shown in Table-1.
Ｌ絞■□２
実施例４の触媒の形状を、外径７ｍｍ、長き７ｍｍの円
柱状に成型した以外は実施例４と全く同様にして反応を
行なった。反応条件及び結果を表−１に示した。L-diameter ■□2 A reaction was carried out in exactly the same manner as in Example 4, except that the catalyst of Example 4 was molded into a cylindrical shape with an outer diameter of 7 mm and a length of 7 mm. The reaction conditions and results are shown in Table-1.
［発明の効果］ 本発明の方法により、以下の優れた効果が得られた。[Effect of the invention] By the method of the present invention, the following excellent effects were obtained.
（１）貫通部分を有する触媒にしたことにより、触媒層
の圧力損失が小さくなり、原料アルカノールアミン分圧
を小さくでき生成物アジリジン化合物の収率が向上した
。(1) By using a catalyst having a penetrating portion, the pressure loss in the catalyst layer was reduced, the partial pressure of the raw material alkanolamine was reduced, and the yield of the product aziridine compound was improved.
（２）反応は吸熱反応であり、高活性を得るには触媒層
の伝熱を良＜シ温度分布をできるだけ小さくするほうが
よいが、貫通部分を有する触媒にしたことにより円柱状
触媒に比べ触媒粒子内の伝熱がよくなり温度分布が小さ
くなって活性が向上した。(2) The reaction is an endothermic reaction, and in order to obtain high activity it is better to improve the heat transfer in the catalyst layer and minimize the temperature distribution as much as possible. Heat transfer within the particles improved, temperature distribution became smaller, and activity improved.
（３）貫通部分を有する触媒にしたことにより原料及び
生成物の拡散距離は短くなり、触媒内部での原料及び生
成物の濃度分布の差が小さくなって逆反応が抑えられ、
アジリジン化合物の選択性が向上した。(3) By using a catalyst with a penetrating portion, the diffusion distance of raw materials and products is shortened, and the difference in the concentration distribution of raw materials and products inside the catalyst is reduced, suppressing reverse reactions.
The selectivity of aziridine compounds was improved.
第１図及び第２図は、本発明によるアジリジン化合物の
製造用触媒の形状を示す。
Ｄ−外径
Ｌ −長さ
Ｗ−肉厚1 and 2 show the shape of a catalyst for producing an aziridine compound according to the present invention. D - Outer diameter L - Length W - Wall thickness
Claims (2)
子内脱水反応せしめて一般式（Ｂ）▲数式、化学式、表
等があります▼（Ｂ） （式中のＲ、Ｒ’は各々式（Ａ）と同じで ある。） で表されるアジリジン化合物を製造するに際し、該アル
カノールアミンを高温、減圧下で、外径３〜１０ｍｍ、
長さが外径の０．５〜２．０倍の円柱の外形を有し、か
つその縦軸方向にその体積が全体の１０％〜８０％の範
囲である貫通部分を有する形状の触媒を用いることを特
徴とするアジリジン化合物の製造方法。(1) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (R and R' in the formula are each selected from hydrogen, methyl group, and ethyl group.) Alkanol represented by The amine is subjected to a gas phase intramolecular dehydration reaction in the presence of a catalyst to produce the general formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) (R and R' in the formula are the same as in formula (A)). ) When producing the aziridine compound represented by
A catalyst having a cylindrical outer shape with a length of 0.5 to 2.0 times the outer diameter and a penetrating portion whose volume is in the range of 10% to 80% of the total in the longitudinal axis direction. A method for producing an aziridine compound, characterized in that it is used.
範囲である請求項（１）に記載の方法。(2) The method according to claim (1), wherein the reaction pressure is in the range of 10 to 200 mmHg in absolute pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63293665A JPH0745463B2 (en) | 1988-11-22 | 1988-11-22 | Method for producing aziridine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63293665A JPH0745463B2 (en) | 1988-11-22 | 1988-11-22 | Method for producing aziridine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02142766A true JPH02142766A (en) | 1990-05-31 |
| JPH0745463B2 JPH0745463B2 (en) | 1995-05-17 |
Family
ID=17797665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63293665A Expired - Fee Related JPH0745463B2 (en) | 1988-11-22 | 1988-11-22 | Method for producing aziridine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745463B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011184194A (en) * | 2010-03-04 | 2011-09-22 | Isao Mikami | Adhesive tape cutter |
| JP2012192337A (en) * | 2011-03-16 | 2012-10-11 | Nippon Shokubai Co Ltd | Catalyst for producing aziridine, and method for producing aziridine using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011224551A (en) * | 2010-03-30 | 2011-11-10 | Nippon Shokubai Co Ltd | Catalyst for producing aziridine compound, and method for producing the aziridine compound using the catalyst |
-
1988
- 1988-11-22 JP JP63293665A patent/JPH0745463B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011184194A (en) * | 2010-03-04 | 2011-09-22 | Isao Mikami | Adhesive tape cutter |
| JP2012192337A (en) * | 2011-03-16 | 2012-10-11 | Nippon Shokubai Co Ltd | Catalyst for producing aziridine, and method for producing aziridine using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745463B2 (en) | 1995-05-17 |
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